Light-Directed Electrochemical Patterning of Copper Structures

ABSTRACT

A method creating a patterned film with cuprous oxide and light comprising the steps of electrodepositing copper from a solution onto a substrate; illuminating selected areas of said deposited copper with light having photon energies above the band gap energy of 2.0eV to create selected illuminated sections and non-illuminated sections; and stripping non-illuminated sections leaving said illuminated sections on the substrate. An additional step may include galvanically replacing the copper with one or more noble metals.

RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 16/327,732 filed onFeb. 22, 2019, which is a U.S. 371 National Phase of PCT/US2017/049187filed on Aug. 29, 2017, which claims the benefit of U.S. ProvisionalApplication No. 62/380,911 filed Aug. 29, 2016, and herein incorporatedby reference.

FIELD OF THE INVENTION

Cuprous oxide (Cu₂O) is considered to be an ideal semiconductor forsolar or photoelectrochemical cells because it has a small (2.0 eV),direct band gap, is composed of inexpensive and earth abundantmaterials, and can be synthesized by electrodeposition or oxidation ofCu metal. Copper and its oxides are also an interesting material systembecause it can easily be oxidized, reduced, or dissolvedelectrochemically by choice of electrochemical potentials and pH ofaqueous solution.

Copper is also an important material for developing and patterningcircuits. A current practice to pattern copper in circuits utilizesexpensive photolithography or direct-write methods like laser ablation.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the present invention provides an inexpensive methodto pattern copper and oxide structures using direct lithographicprocesses driven by illumination. This eliminates the need for expensivelasers, photoresist chemistry, or chemical/physical vapor depositionfacilities. It requires low power and illumination coherenceconstraints, making it an inexpensive alternative to current methods.Moreover, as copper is an increasingly expensive raw material, all ofthe copper not used in the patterning is available for other uses.

In another embodiment, the present invention provides patterning viadirect illumination with no expensive photosensitive chemistry required.

In yet another embodiment, the present invention provides an inexpensiveelectrodeposition process, with no expensive evaporation processesrequired.

In yet another embodiment, the present invention provides an inexpensiveelectrodeposition process, with no expensive vacuum processes required.

In another embodiment, the present invention provides patterningprocesses which use incoherent light sources which reduce the need forhigh-power lasers to perform patterning.

In another embodiment, the present invention provides methods forpatterning copper that may be generalizable to any conductive substrate(not just transparent ones).

In another embodiment, the present invention provides methods that usedark and transparent Cu₂O which are chemically distinct phases topattern thin films features including sub-millimeter features.

In yet another embodiment, the present invention provides methods thatgalvanically replaces deposited Cu₂O pattern with one or more metalssuch as noble metals to create a pattern consisting of the substitutedmetal or metals. In a preferred embodiment, the metal is a noble metal.

In another embodiment, the present invention provides methods thatdirect write copper-based structures on electrodes to either patternregions of Cu₂O or to pattern conductive Cu patterns for circuits thatreplace photolithography in compatible materials systems, which is thecurrent method by which copper is patterned.

Additional objects and advantages of the invention will be set forth inpart in the description which follows, and in part will be obvious fromthe description, or may be learned by practice of the invention. Theobjects and advantages of the invention will be realized and attained bymeans of the elements and combinations particularly pointed out in theappended claims.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, which are not necessarily drawn to scale, like numeralsmay describe substantially similar components throughout the severalviews. Like numerals having different letter suffixes may representdifferent instances of substantially similar components. The drawingsillustrate generally, by way of example, but not by way of limitation, adetailed description of certain embodiments discussed in the presentdocument.

FIG. 1 is a schematic of a deposition procedure that may be used for anembodiment of the present invention.

FIG. 2A provides an example of direct illuminated writing of blackcuprous oxide (illuminated area) and plain, yellow cuprous oxide (maskedarea) via potentiostatic electrodeposition for an embodiment of thepresent invention.

FIG. 2B illustrates a reflection image of direct illuminated writing ofcuprous oxide (illuminated area) with cathodic electrodeposition/anodicdissolution for an embodiment of the present invention.

FIG. 2C illustrates a back-illuminated image of direct illuminatedwriting of cuprous oxide (illuminated area) with cathodicelectrodeposition/anodic dissolution for an embodiment of the presentinvention.

FIG. 3A is a schematic of the photolithographic patterning of Cu₂O on aconductive surface for an embodiment present invention.

FIG. 3B depicts the galvanic replacement of Cu₂O with Au, Ag, or othernoble metals that spontaneously form on the surface while oxidizing theCu₂O back to soluble Cu2+ ions for an embodiment present invention.

FIG. 4A shows a time series of Cu 2p and spectra for Cu₂O filmssubmerged in a Galvanic replacement reaction (GRR).

FIG. 4B shows a time series of Au 4f XPS spectra for Cu₂O filmssubmerged in 5 mM NaAuCl4 GRR solution for an embodiment presentinvention.

FIG. 5A is a comparison of Cu 2p spectra for Cu₂O films submerged in anaqueous buffer for an embodiment present invention.

FIG. 5B is a comparison of Au 4f XPS spectra for Cu₂O films submerged inan aqueous buffer for an embodiment present invention.

FIG. 6A is a SEM micrograph of the nanoscale of GRR-deposited Au on Cu2Oafter 5-minute exposure for an embodiment present invention.

FIG. 6B is a SEM micrograph of the nanoscale microstructure ofGRR-deposited Au on Cu2O after 5-minute exposure for an embodimentpresent invention.

FIG. 7A illustrates GRR-deposited Au on Cu₂O without illumination asshown in FIG. 4A.

FIG. 7B illustrates GRR-deposited Au on Cu₂O with 455 nm LEDillumination but without NaAuCl4 in the solution for an embodimentpresent invention.

FIG. 7C illustrates GRR-deposited Au on Cu₂O and with 455 nm LEDillumination and with NaAuCl4 in the solution for an embodiment presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

Detailed embodiments of the present invention are disclosed herein;however, it is to be understood that the disclosed embodiments aremerely exemplary of the invention, which may be embodied in variousforms. Therefore, specific structural and functional details disclosedherein are not to be interpreted as limiting, but merely as arepresentative basis for teaching one skilled in the art to variouslyemploy the present invention in virtually any appropriately detailedmethod, structure or system. Further, the terms and phrases used hereinare not intended to be limiting, but rather to provide an understandabledescription of the invention.

As shown in FIG. 1, in one embodiment of the present invention, cuprousoxide (Cu₂O) 100 can be electrodeposited from a solution of coppersulfate by using a potentiostat 102, light source 110 which may be alight emitting diode that is used to create a light pattern 112,electrolyte solution 114, and mask 116A-116E which may be transparent.Also provided are electrode 120, which may be transparent ornon-transparent, reference electrode (RE) 122, and counter electrode(CE) 124.

In a preferred embodiment, cuprous oxide (Cu₂O) can be electrodepositedfrom a solution of copper sulfate and lactic acid, adjusted to basic pH(9-13) with sodium hydroxide. The electrodeposition is carried out on aconductive substrate like fluorine-doped tin oxide on glass,metal-coated substrates like evaporated gold on glass, or a siliconwafer as well as other substrates to which the metal will adhere.

As shown, a cathodic potential is applied to the electrode in solution(roughly −0.4V vs. Ag/AgCl reference electrode) to reduce the copperions in solution and form the solid Cu₂O phase as a thin-film coating onthe surface of the electrode. Cuprous oxide is synthesized as itshole-doped, p-type photoactive phase in this process. Moreover, it is aphotocathode, meaning that the minority carrier electrons that aretransferred at the interface to drive the electrodeposition can also beexcited by light absorption to drift to the interface.

It has been found that the electrons are energetic enough to reduce Cu₂Oon the surface to Cu as a method of photodoping. As a result, theregions of the thin film grown under illumination are visibly andchemically different than the regions grown without illumination asshown in FIGS. 2A-2C.

FIG. 2A provides an example of direct illuminated writing of blackcuprous oxide (illuminated area) 200 and plain, yellow cuprous oxide(masked area) 202 via potentiostatic electrodeposition for an embodimentof the present invention. FIG. 2B illustrates a reflection image ofdirect illuminated writing of cuprous oxide (illuminated area) 210 withcathodic electrodeposition/anodic dissolution for an embodiment of thepresent invention.

FIG. 2C illustrates a back-illuminated image of direct illuminatedwriting of cuprous oxide (illuminated area) 220 with cathodicelectrodeposition/anodic dissolution for an embodiment of the presentinvention. As a result, the methods provided by the present inventionprovide methods to grow copper structures patterned by illumination.

The electrode can be switched between the cathodic (depositing)potential and a slightly anodic (dissolving) potential. The illuminationof the pattern may occur during, before or in-between switching. Due tothe photodoping of grown films, the areas under illumination or thathave been illuminated, during this potential step procedure remain whilethe areas not under illumination or not subject to illumination arestripped away by dissolution.

Patterning the light via a transparency mask allows for the patterningof regions of photodoped Cu₂O, and therefore the two-dimensionalstructure of the thin film on the electrode surface. In one embodiment,the conductive interface may be a transparent fluorine-doped tin oxideon glass electrode.

A number of different methods may be used to create the patterns. In theembodiment shown in FIG. 1, pattern 100 is formed on a first surface ofsubstrate 120 while mask 116 is located on an opposingly located secondsurface. For this embodiment, light source 110 and mask 116 are used tocreate patterns of light that are transmitted through transparentsubstrate 120. This creates the illumination patterns that alter theCu₂O. In other words, the backside of the substrate is illuminated forthis embodiment. Patterns may then be created as described above.

As shown in FIG. 3A, pattern 300 may be created from illuminating thefront side of the substrate 306. For this embodiment, patterning fromthe front allows for the use of non-transparent substrates and alsoallows for the patterning to occur on the growing interface 304. Topromote the growth of the Cu₂O pattern, mask 310 needs to be located aspaced distance away from growing surface 304 so as to not block thesolution from reaching surface 304. Patterns may then be created asdescribed above.

In yet another embodiment of the present invention, a projector may beused to create the illumination patterns from either the front side orbackside. This would eliminate the need to use mask 116 or 301. Patternsmay then be created as described above. In other embodiments, theprojection source can be used to produce a time-dependent,two-dimensional illumination pattern (like an image) that changes whilethe film is grown to add three-dimensional structure to the film. Underconstant cathodic electrodeposition potential, changing the illuminationpatterns, by time, intensity, color of the illumination, or anycombination of these three illumination parameters as a dynamicalillumination image creates a three-dimensional, photodoped “black” Cu₂Ostructure into the thin film. Under the cathodicelectrodeposition/anodic dissolution work cycle, this can result into aprinted three-dimensional structure of Cu₂O on the electrode surface. Ineither case, portions of the deposited film can be removed by chemicaldissolution or through electrochemical stripping during growth toproduce a thin film patterned in three dimensions. This method could beused to grow three-dimensional templates (like stamps or molds),structured electrocatalysts, three-dimensional circuits, metamaterials(nanostructured materials with non-intuitive optical properties, likenegative refractive index or generation of strange polarizations), ornanotextured, low-friction tribological surfaces.

FIGS. 3A and 3B also show a two-step scheme for the solution-phaselight-directed patterning of noble metal surfaces based on thephotolithographic properties of Cu₂O for another embodiment of thepresent invention. As shown in FIG. 3A, photolithographic patterning ofCu₂O 300 and 302 on a conductive surface 304 and substrate 306 may beaccomplished as described above through the use of a mask andillumination source.

The patterned film may be fabricated, in a preferred embodiment, with anelectrochemical duty cycle of cathodic Cu₂O deposition followed byanodic dissolution. The remaining Cu₂O is the portion of the film thatwas exposed to light during growth. The steps of depositing,illuminating and dissolution may be repeated.

The second step of the embodiment is shown in FIG. 3B. As shown, thisstep utilizes the galvanic replacement of Cu₂O 300 and 302 with Au, Ag,or other noble metals 350A-350F that spontaneously form on the surfacewhile oxidizing the Cu₂O back to soluble Cu2+ ions.

The present invention may be used to fabricate integrated circuits,print interconnections between electrical components, performthree-dimensional patterning of circuits, provide direct writelithography masks, pattern semiconductor structures for photovoltaics orphotoelectrochemical cells, electrocatalyst patterning, controlling thecomposition of multi-metal electrocatalysts, photodoping Cu2O to formelectrodeposited PN junctions for electrical diodes and photovoltaics,microelectrode patterning for dry cell batteries (via low temp oxidationto CuO).

In still other embodiments, the present invention provides a method topattern the local doping/chemistry of thin films of cuprous oxide withlight. By illuminating cuprous oxide with photon energies above the bandgap energy of 2.0 eV, the illuminated area of the cuprous oxide thinfilm is increasingly darkened with increasing intensity duringelectrodeposition. By stepwise scanning of the electrode potential, thearea of the thin film not under illumination can be stripped from theelectrode, leaving the remaining illuminated areas on the electrode orconductive surface. This process allows for directly writingcopper-based structures on electrodes to either pattern regions of Cu₂Osemiconductor or to pattern conductive Cu patterns for circuits. The Cupatterns may then be replaced with one or more noble metals as describedabove.

In one application of the the present invention, Cu₂O films weresubmerged in 5 mM NaAuCl4 GRR solution (pH 2.7) for 0 s, 10 s, 1 min, 2min, and 60 min. The Cu 2p spectra show that the starting Cu₂O surfacequickly oxidizes to CuO. Eventually all of the CuO/Cu₂O dissolves asindicated by the lack of the Cu XPS features after 60 min. A Cu₂O filmthat was air-annealed (400 C for 1 hour) to CuO still showed the CuO XPSfeatures after 60 minutes in the Au solution. The Au 4f spectra showthat Au begins to deposit within the first 10 s of exposure andincreases intensity. The CuO film shows no Au deposition after 60minutes.

FIGS. 5A and 5B are comparisons of Cu 2p and Au 4f XPS spectra for Cu₂Ofilms submerged in an aqueous buffer (pH 2.7) with 10 s, 1 min andwithout NaAuCl4. Plain, unexposed Cu₂O is shown for reference. The Cu 2pspectra show that without NaAuCl4 in the solution, the Cu₂O surfacemaintains its oxidation state through dissolution. The solid-stateoxidation to CuO only occurs in the presence of AuCl4(-) reduction.

FIGS. 6A and 6B are SEM micrographs of the nanoscale morphology andmicrostructure of GRR-deposited Au on Cu₂O after a 5-minute exposure.

FIG. 7A illustrates GRR-deposited Au on Cu₂O without illumination asshown in FIG. 4A. FIG. 7B illustrates GRR-deposited Au on Cu₂O with 455nm LED illumination but without NaAuCl4 in the solution. FIG. 7Cillustrates GRR-deposited Au on Cu₂O and with 455 nm LED illuminationand with NaAuCl4 in the solution.

In yet other embodiments, the present invention provides methods forcreating patterns by electrodeposition that are not limited to Cu₂O, butinclude other materials that may be deposited by electrodeposition. In apreferred method, a film of photoactive material having anelectrodeposition polarity that matches its photoactive polarity isdeposited in two ways. First by electrodeposited and by the applicationof light. The light acts as an additional bias which results inadditional deposition of material. Thus, in areas of the illumination,the deposition rate of material is greater that in the non-illuminatedareas, creating a pattern of areas with more deposited material ascompared to the non-illuminated areas.

In circumstances where the desired pattern is to include areas ofdeposited material and areas where there is no deposited material, theillumination may be continued during the reversal of the polarity.Reversing the polarity causes dissolution of the deposited material.Non-illuminated areas have a higher rate of dissolution than theilluminated areas since the illumination reverses or retards themagnitude of the reverse polarity. Thus, non-illuminated areas arestripped of deposited material at a higher rate and will have allmaterial removed prior to the removal of all material from theilluminated areas.

While the foregoing written description enables one of ordinary skill tomake and use what is considered presently to be the best mode thereof,those of ordinary skill will understand and appreciate the existence ofvariations, combinations, and equivalents of the specific embodiment,method, and examples herein. The disclosure should therefore not belimited by the above described embodiments, methods, and examples, butby all embodiments and methods within the scope and spirit of thedisclosure.

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 18. A method of creating a pattern on asubstrate using electrodeposition and light comprising the steps of: onselected areas of said substrate, depositing material byelectrodeposition and by illumination to create a deposition rate ofmaterial that is greater than in the non-illuminated areas; andreversing the polarity while maintaining the illumination of saidselected areas to cause said non-illuminated areas to have a higher rateof dissolution than said selected areas.
 19. The method of claim 18wherein said deposited material is copper.
 20. The method of claim 18wherein said illumination is changed by time to create three-dimensionalpatterns.
 21. The method of claim 18 wherein said illumination ischanged by intensity to create three-dimensional patterns.
 22. Themethod of claim 18 wherein said illumination is changed by color of theillumination to create three-dimensional patterns.
 23. The method ofclaim 18 wherein said illumination is changed by a combination of colorof the illumination, time or intensity to create three-dimensionalpatterns.